JP7341687B2 - Method for producing refined oils and fats, and refined oils and fats - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing refined oils and fats, and to refined oils and fats.

In recent years, consumers' interest in food quality has been increasing. The subject of interest also extends to edible oils and fats used in the production of processed foods (fried foods, etc.).

It is known that fats and oils deteriorate when exposed to heat, light, and the like. When fats and oils are exposed to heat and light, hydrolytic deterioration occurs in the presence of moisture, and oxidative deterioration occurs in the presence of oxygen. As a result of deterioration, the acid value of fats and oils increases, and flavor and color deteriorate. In particular, in the production of fried foods (fries, tempura, fried chicken, etc.), cooking is carried out using fats and oils heated to around 180°C. ), it is required to suppress deterioration due to heating.

For example, the "Specifications and Standards for Foods, Additives, etc. (Ministry of Health and Welfare Notification No. 370 of 1950)" states that instant noodles (equivalent to fried noodles) must have an acid value of more than 3 or It is specified that the peroxide value must not exceed 30.

Further, there may be a problem that the color tone of the frying fat becomes darker due to deterioration of the frying fat due to heat or the like. When the color tone of the frying oil becomes dark, fried foods produced using the oil and fat are also colored, and the appearance is impaired.

For example, Patent Document 1 describes a method for producing edible fats and oils that is made to react with a silica/magnesia-based preparation before being deodorized (steam distillation) at 140 to 190°C.

Unexamined Patent Publication No. 2014-12

However, in the method of Patent Document 1, the acid value of the refined oil and fat is 0.02 or more, as shown in the examples. Furthermore, if the conditions of the deodorizing step in Patent Document 1 were made more severe, free fatty acids would be removed, but on the other hand, hydrolysis of fats and oils would proceed due to water vapor and free fatty acids would be generated, resulting in an acid value of 0.01 or less. It's difficult to become.

The present invention has been made in view of the above situation, and an object of the present invention is to provide a technology that can reduce the acid value of refined oils and fats and suppress the increase in acid value and/or heat discoloration during frying.

The present inventors have discovered that the above problems can be solved by performing an adsorption step in which liquid fats and oils are brought into contact with a silica/magnesia-based preparation at a temperature below 80°C after the deodorizing step, and have completed the present invention. Ta. Specifically, the present invention provides the following.

(1) A method for producing refined fats and oils, which includes, after a deodorizing step, an adsorption step in which liquid fats and oils are brought into contact with a silica/magnesia-based preparation at a temperature below 80°C.
(2) The method for producing refined fats and oils according to (1), wherein the silica-magnesia-based preparation is a composite adsorbent of silicon dioxide particles and magnesium oxide particles.
(3) The method for producing refined fats and oils according to (1) or (2), wherein the acid value of the fats and oils subjected to the adsorption step is 0.2 or less.
(4) The method for producing refined fats and oils according to any one of (1) to (3), which includes a step of bringing the fats and oils into contact with ozone before the deodorizing step.
(5) The method for producing refined fats and oils according to any one of (1) to (4), wherein the step of contacting with water vapor at 140° C. or higher is not performed after the adsorption step.
(6) The method for producing refined fats and oils according to any one of (1) to (5), wherein the adsorption step involves passing the fats and oils in a liquid state through a container filled with a silica-magnesia-based preparation.
(7) The method for producing refined fats and oils according to any one of (1) to (6), wherein the refined fats and oils that have undergone the adsorption step have an acid value of 0.00 to 0.01.
(8) A refined fat or oil having an acid value of 0.00 to 0.01, which has been produced by the method for producing refined fat or oil according to any one of (1) to (7).
(9) Refined fats and oils having an acid value of 0.001 to 0.008.

According to the present invention, a technique for producing refined fats and oils having a sufficiently low acid value, and a technique for suppressing an increase in acid value and/or heat discoloration during frying are provided. Furthermore, flavor stability is also improved by bringing the oil into contact with ozone.

Embodiments of the present invention will be described in detail below. Note that the present invention is not limited to the following embodiments. Furthermore, in this specification, "A (numerical value) to B (numeric value)" means "above A and below B", and the ratio means mass percentage.

<Method for producing refined oils and fats>
In the method for producing refined fats and oils of the present invention, after the deodorizing step, an adsorption step is performed in which the liquid fats and oils are brought into contact with a silica/magnesia-based preparation at a temperature below 80°C.

(Oils and fats)
The fats and oils used in the method for producing refined fats and oils of the present invention may be those used as edible fats and oils. Examples include animal and vegetable oils, oils and fats synthesized from glycerin and fatty acids, fractionated oils thereof, transesterified oils, hydrogenated oils, and the like. Also included are individual fats and oils and blends of a plurality of fats and oils.
Examples of animal and vegetable oils include soybean oil, rapeseed oil, high-oleic rapeseed oil, sunflower oil, high-oleic sunflower oil, olive oil, safflower oil, high-oleic safflower oil, corn oil, cottonseed oil, rice oil, sesame oil, perilla oil, and linseed oil. , peanut oil, grapeseed oil, beef tallow, milk fat, fish oil, coconut oil, palm oil, palm kernel oil and the like.
Examples of fats and oils synthesized from glycerin and fatty acids include medium chain fatty acid triglycerides (MCT).
Examples of the fractionated oil include fractionated oils of palm oil such as palm olein, palm super olein, palm stearin, and palm midfraction.
As the transesterified oil, transesterified oil of palm oil or fractionated oil of palm oil and other liquid fats and oils, or transesterified oil of MCT and vegetable oil, etc. can be used.
Examples of hydrogenated oils include hydrogenated oils such as animal and vegetable oils and fractionated oils of animal and vegetable oils, as well as hydrogenated oils such as transesterified oils.

In the method for producing refined fats and oils of the present invention, the fats and oils to be subjected to the deodorizing process are unrefined fats and oils, semi-refined fats and oils that have undergone a process selected from a degumming process, a deacidification process, a decoloring process, a dewaxing process, etc., or a deodorized fat and oil. Refined fats and oils (deodorized fats and oils) that have undergone a process selected from a gum process, a deacidification process, a decolorization process, a dewaxing process, etc. and a deodorization process can be used. Further, refined oils and fats that have been subjected to a process selected from a degumming process, a deoxidizing process, a decoloring process, a dewaxing process, etc. can also be used. Note that one of the purposes of the present invention is to provide oils and fats with sufficiently low acid values; however, the acid value can be lowered by the deodorizing process and adsorption process described later, so the deoxidizing process is not necessarily essential. do not have. When the deoxidizing process is performed, the load of the deodorizing process can be reduced. Furthermore, in the case of significantly colored fats and oils, it is preferable to use fats and oils that have undergone a decolorization process.

(Deodorizing process)
The method for producing refined fats and oils of the present invention includes an adsorption step in which liquid fats and oils are brought into contact with a silica/magnesia-based preparation at a temperature below 80° C., but a deodorizing step is performed before this adsorption step. There is no particular problem with the conditions for the deodorizing process as long as they are within the range of deodorizing conditions that are used in normal refining of fats and oils, but it is preferable that the acid value of the fats and oils that have undergone the deodorizing process (deodorized fats and oils) is 0.2 or less. . The lower the acid value, the higher the effect of the adsorption step, and the acid value of the refined oil and fat can be sufficiently reduced. It is more preferable that the acid value of the oil or fat that has undergone the deodorization step is 0.1 or less.

In the present invention, the acid value is a value measured in accordance with "Standard Oil and Fat Analysis Test Method 2.3.1-2013 Acid Value" established by the Japan Oil Chemists' Society. Acid value indicates the amount of free fatty acids contained in fats and oils, and is expressed in mg of potassium hydroxide required to neutralize 1 g of sample oil.

The conditions for the deodorizing step are not particularly limited, but for example, the deodorizing temperature is 180 to 280°C, the degree of vacuum is 100 to 800 Pa, the amount of water vapor is 0.3 to 10% by mass (based on fats and oils), and the deodorizing time is 30 to 120 minutes. A range is preferred. The deodorizing temperature is more preferably 200 to 270°C, even more preferably 230 to 260°C, and most preferably 240 to 250°C. The degree of vacuum is more preferably 200 to 600 Pa, and even more preferably 300 to 500 Pa. The amount of water vapor is more preferably 1 to 8% by mass (based on oil), even more preferably 1 to 5% by mass (based on oil), and most preferably 1 to 3% by mass (based on oil). The deodorizing time is more preferably 40 to 120 minutes, even more preferably 40 to 80 minutes.

In addition, in the deodorizing process, citric acid may be added at the end of the deodorizing process. Addition of citric acid increases oxidative stability. Citric acid is preferably added in an amount of 10 to 50 ppm, more preferably 26 to 50 ppm, based on the deodorized oil or fat. Note that since citric acid does not disperse or dissolve in oil as it is, it is preferably added as an aqueous solution of 5 to 20% by mass.

(Adsorption process)
The method for producing refined fats and oils of the present invention includes an adsorption step after the deodorizing step. Although another step can be performed between the deodorizing step and the adsorption step, it is preferable that the next step after the deodorizing step is an adsorption step. In addition, since the adsorption step is performed at a temperature below 80° C., the adsorption step may be performed after cooling, storage, etc., if necessary. The silica/magnesia-based preparation used in the adsorption process is a preparation of silica (silicon dioxide) and magnesia (magnesium oxide), and is a mixture of silica particles and magnesia particles dispersed and mixed. For example, the mass ratio of silica to magnesia is preferably 1:5 to 3:1. Further, as a silica/magnesia-based preparation, a preparation consisting of a combination of silicon dioxide, magnesium oxide, and water can be used, for example, 30 to 80% by mass of silicon dioxide, 10 to 50% by mass of magnesium oxide, and 5 to 20% by mass of water. % composition is preferred. These silica/magnesia-based preparations, for example, are made by dispersing silica and magnesia particles in water as nano-order unit particles without dissolving them, and then uniformly mixing them, which involves the exchange and recombination of atoms between particles. They can be obtained by combining and forming a tight complex without forming any chemical bonds. Moreover, a commercially available product ("Mizuka Life", manufactured by Mizusawa Chemical Industry Co., Ltd.) can also be used.

The method for producing refined fats and oils of the present invention includes an adsorption step in which the above-mentioned fats and oils are brought into contact with a silica/magnesia-based preparation at a temperature below 80°C. In addition to free fatty acids in fats and oils, the contact can remove components (promoting substances) that increase the acid value during frying, coloring substances, or substances that promote coloring. Note that fats and oils are naturally derived, and at present, components other than free fatty acids that increase the acid value, some coloring substances, or substances that promote coloration have not been identified.

If the fat is in a liquid state, sufficient contact efficiency with the silica/magnesia-based preparation can be obtained. Furthermore, if the contact temperature is 80° C. or higher, the silica/magnesia-based preparation alters the trace components of the oil and fats and generates a foreign odor, so a deodorizing step (steam distillation) is essential. However, when a deodorizing step is performed after the adsorption step, hydrolysis occurs slightly, making it difficult to obtain refined fats and oils with a low acid value. Therefore, the contact temperature is preferably in the range of -10 to 79°C, -5 to 75°C, 0 to 60°C, 5 to 60°C, or 5 to 50°C, more preferably 5 to 40°C, and 10 to 30°C. C is most preferred.

The contact between the fat and oil and the silica-magnesia-based preparation can be carried out by adding the silica-magnesia-based preparation to the fat and oil, stirring, and then filtration or centrifugation. Furthermore, a method in which liquid oil is passed through a container filled with a silica/magnesia preparation is simple and preferable. For example, a silica-magnesia-based preparation can be packed into a filter (single-disc filter, filter press, leaf filter, etc.), column, etc., and the oil and fat can be brought into contact with it by passing the liquid therethrough. In particular, it is more preferable to pass the liquid through a cartridge-type filter filled with a silica-magnesia-based preparation.

Oils and fats that have gone through the deodorizing process have a small adsorption amount of silica/magnesia-based preparations such as free fatty acids, so even short-term contact such as filtration or the use of a very small amount of silica/magnesia-based preparations are sufficient. . Therefore, the contact time between the fat and oil and the silica/magnesia preparation and the amount of the silica/magnesia preparation used are not particularly limited. The contact time between the fat and oil and the silica/magnesia-based preparation is preferably 0.5 minutes or more, more preferably 5 minutes or more, even more preferably 15 minutes or more, and most preferably 30 minutes to 3 hours. Further, the amount of the silica/magnesia-based preparation used is preferably 0.05 parts by mass or more per 100 parts by mass of fats and oils, more preferably 0.1 to 5 parts by mass per 100 parts by mass of fats and oils, and more preferably The amount is preferably 0.5 to 3 parts by mass per 100 parts by mass of fats and oils.

(Post-adsorption process)
In the method for producing refined fats and oils of the present invention, the refining step is completed with the above-mentioned adsorption step, but additional refining steps, fractionation steps, mixing steps (addition steps), etc. may be performed as necessary. However, when the process of contacting with water vapor at 140°C or higher, such as the deodorizing process, causes a small amount of hydrolysis of the oil and fat, and on the other hand, free fatty acids are removed by distillation, resulting in an equilibrium of the amount of free fatty acids in the oil. Since the condition is such that the acid value of the oil or fat exceeds 0.01, it is preferable not to perform this step.

(Process of bringing oil and fat into contact with ozone)
In the present invention, the flavor stability of refined fats and oils is improved by passing through the process of bringing the fats and oils into contact with ozone and then the deodorizing process. In particular, flavor deterioration due to exposure to light can be suppressed. It is thought that the process of bringing fats and oils into contact with ozone converts the substances that cause the exposure odor into compounds that are easily decomposed by decomposition or distillation. Ozone is a gas composed of three oxygen atoms, and can be brought into contact with oil or fat by bringing ozone gas into contact with oil or fat, or by stirring water containing ozone with oil or fat. Since it is not necessary to remove components other than ozone after contacting with ozone, it is preferable to bring ozone gas into contact with fats and oils. Examples of methods for bringing ozone gas into contact with fats and oils include a method in which degassed fats and oils are brought into contact with ozone gas, a method in which ozone gas is brought into contact by bubbling in fats and oils, and a method in which contact is brought into contact with water containing ozone. be able to. The ozone generator is not particularly limited, but it is possible to use a device that generates ozone by the collision of high-energy electrons and oxygen molecules, such as ultraviolet irradiation in the air or silent discharge in oxygen. can. Also, commercially available products used for sterilizing, deodorizing, and decolorizing water, foods, etc. can be used.

The longer the contact between the fat and oil and ozone, the higher the effect of improving exposure odor, and the contact time is preferably 1 minute or more, and more preferably 2 minutes to 24 hours. It is more preferable that the fat and oil be brought into contact with ozone for 3 minutes to 6 hours, and it is even more preferable that the fat and oil be brought into contact with ozone for 10 minutes to 2 hours. Further, since the contact temperature brings ozone and fat into contact with each other, it may be any temperature at which the fat or oil is in a liquid state, and is preferably -10°C or higher, and more preferably 5°C or higher. In addition, if the contact temperature becomes high, the oxidation reaction of the oil or fat will be promoted and control of the reaction will become difficult, so the contact temperature is preferably 180°C or lower, more preferably 100°C or lower. The contact temperature is more preferably 10 to 60°C, most preferably 10 to 40°C.

As for the amount of ozone, it is sufficient that ozone can be dissolved in the fats and oils, and it is preferable that ozone is supplied to the fats and oils in an amount of 0.0002% by mass or more during the contact time, or ozone is supplied to the fats and oils in an amount of 0.0002% by mass or more during the contact time. It is preferable that 0.0004% by mass or more is supplied. It is more preferable that 0.0022% by mass or more of ozone is supplied to the fat and oil during the contact time, and even more preferably that 0.006% by mass or more of ozone is supplied to the fat and oil. It is more preferable that ozone is supplied in an amount of 0.005 to 0.65% by mass, and most preferably that ozone is supplied in an amount of 0.006 to 0.65% by mass based on the fat or oil.

<Refined fats and oils>
The refined oil and fat of the present invention has an acid value of 0.00 to 0.01 after passing through the above-mentioned method for producing refined oil and fat. Note that fats and oils are naturally derived, and at present, components that increase the acid value other than free fatty acids and some coloring substances or substances that promote coloration have not been identified. In order to identify refined oils and fats that have the effect of suppressing the rise in acid value and/or coloration caused by heating, a product-by-process format was used. Note that an acid value of 0.00 to 0.01 is a range that cannot be achieved only by a normal deoxidizing process or deodorizing process.
The acid value is more preferably 0.001 to 0.008.

(Other ingredients)
Other components can be added to the refined fat and oil to the extent that they do not impair the effects of the present invention, and the types and amounts of the components to be blended can be appropriately set depending on the desired effect. These components are, for example, components used in common fats and oils (food additives, etc.). These components include, for example, antioxidants, antifoaming agents, emulsifiers, etc., and are preferably added after the deodorizing step and before filling.
Examples of the antioxidant include tocopherols, ascorbic acids, flavone derivatives, kojic acid, gallic acid derivatives, catechin and its esters, fukiic acid, gossypol, sesamol, and terpenes. Silicone oil is mentioned as an antioxidant and antifoaming agent. Examples of the coloring component include carotene, astaxanthin, and the like. The emulsifier is appropriately selected from polyglycerin fatty acid ester, sucrose fatty acid ester, sorbitan fatty acid ester, polysorbate, propylene glycol fatty acid ester, polyglycerin condensed ricinoleate, diacylglycerol, waxes, sterol esters, phospholipids, and the like.
Note that it is preferable that the silicone oil is contained in an amount of 0.5 to 10 mass ppm. The silicone oil preferably has a dimethylpolysiloxane structure and a kinematic viscosity of 100 to 5000 mm ² /s at 25°C. The kinematic viscosity of the silicone oil is more preferably 500 to 2000 mm ² /s, even more preferably 800 to 1100 mm ² /s, and most preferably 900 to 1100 mm ² /s. As the silicone oil, those commercially available for food use can be used. Note that the term "kinetic viscosity" here refers to a value measured in accordance with JIS K 2283 (2000). It is also preferable to use a silicone oil containing fine particle silica in addition to silicone oil.

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples.

<Analysis method>
Analysis in each test was conducted according to the following method.

(Acid value)
The acid value was measured in accordance with "Standard Oil and Fat Analysis Test Method 2.3.1-2013 Acid Value" established by the Japan Oil Chemists' Society. Acid value indicates the amount of free fatty acids contained in fats and oils, and is expressed in mg of potassium hydroxide required to neutralize 1 g of sample oil.

(color tone)
The chromaticity of the test oil was measured using a 0.5-inch cell with a Lovibond colorimeter (trade name "Lovibond PFX995", manufactured by The Tintometer Limited) as yellow chromaticity (Y value) and red chromaticity (Y value). R value) was measured. Based on these results, "Y+10R" was calculated to calculate the color value. The smaller the value of Y+10R, the lighter the color tone, and the larger the value of Y+10R, the darker the color tone.

<Preparation of refined fats and oils 1>
Refined canola oil (acid value 0.04), silica/magnesia-based preparation (manufactured by Mizusawa Chemical Co., Ltd., "Mizuka Life F-2G": approximately 55% silica, approximately 32% magnesia, approximately 13% water), and carbon dioxide. Silicon (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and magnesium oxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were added in an amount of 1% by mass to purified canola oil, stirred at room temperature for 6 hours, and then filtered. Each refined oil was obtained. Table 1 shows the acid value of each refined oil.

As shown in Table 1, the acid value of the refined oil in Example 1 was lower than that in Comparative Examples 1 and 2, and Comparative Examples 1 and 2 had no difference from the Reference Example in which no adsorption treatment was performed.

<Preparation of refined fats and oils 2>
Canola decolorized oil was deodorized at 250° C., 60 minutes, 4.5 torr, and a water vapor content of 3% by mass relative to oil to obtain refined oil A (acid value 0.04, color tone 0.3).

Silicone oil ("KF-96ADF-1,000CS" manufactured by Shin-Etsu Chemical Co., Ltd.) was added to deodorized oil A in an amount of 3 ppm by mass based on refined oil A to obtain refined oil A-1.

Add 1 mass of silica/magnesia-based preparation (manufactured by Mizusawa Chemical Industry Co., Ltd., "Mizuka Life F-2G": approximately 55% silica, approximately 32% magnesia, approximately 13% water) to refined oil A. % was added, stirred at 20° C. for 1 hour, and filtered to obtain purified oil B. Silicone oil ("KF-96ADF-1,000CS" manufactured by Shin-Etsu Chemical Co., Ltd.) was added to refined oil B in an amount of 3 ppm by mass to obtain refined oil B-1.

<Fly test>
4L of each test oil was placed in a fryer and fried for 8 days (8 hours/day). For frying, potato tempura (2 days), croquettes (2 days), and fried chicken (4 days) were prepared in the following order. Table 1 shows the acid value and color tone of the fats and oils after the frying test.
[Imoten]
Every hour, slice 8 sweet potatoes into 1cm thick slices and add batter (tempura powder (product name: Nissin Oishii Tempura Flour, manufactured by Nissin Foods Co., Ltd.): water = 1:1.6). Dip and fry at 180°C for 3.5 minutes.
[croquette]
Every hour, four 70 g croquettes (trade name: "Nichirei Crispy Croquettes (Vegetables)", manufactured by Nichirei Foods Co., Ltd.) were fried at 180° C. for 4.5 minutes.
[fried]
Every hour, 6 pieces of about 35 g of chicken thighs were coated with batter (Karaage powder (product name: Karaage no Moto No. 1, manufactured by Japan Shokuken Co., Ltd.): water = 1:1) and heated to 180°C. Fried for 4 minutes.

As shown in Table 2, it was confirmed that Example 2 had a lower acid value as a refined oil than Comparative Example 3, and that the increase in acid value and heat discoloration after frying were suppressed. .

Claims (6)

A method for producing refined fats and oils, which includes, after a deodorizing step, an adsorption step in which liquid fats and oils with an acid value of 0.2 or less are brought into contact with a silica/magnesia-based preparation at a temperature below 80°C. However, refined fats and oils are not recycled used cooking oil). The method for producing refined fats and oils according to claim 1, wherein the silica-magnesia-based preparation is a composite adsorbent of silicon dioxide particles and magnesium oxide particles. The acid value of the oil and fat to be subjected to the adsorption step is 0.2 or less,
The method for producing refined fats and oils according to claim 1 or 2, wherein the step of contacting with water vapor at 140° C. or higher is not performed after the adsorption step. The method for producing refined fats and oils according to any one of claims 1 to 3, comprising a step of bringing the fats and oils into contact with ozone before the deodorizing step. The method for producing refined fats and oils according to any one of claims 1 to 4, wherein in the adsorption step, the fats and oils in a liquid state are passed through a container filled with a silica-magnesia-based preparation. The method for producing refined fats and oils according to any one of claims 1 to 5, wherein the refined fats and oils that have undergone the adsorption step have an acid value of 0.00 to 0.01.